Composition of matter



Patented Mar. 26, 1940 UNITED STATES PATENT OFFICE ooMPosr'r'IoN 0FMATTER Melvin De Groote, University City, Mo., assignor,

by mesne assignments, to Petrolite Corporation, Ltd, a corporation ofDelaware No Drawing. Application March 10, 1939, Serial No. 261,094

8 Claims.

This application is a continuation in part of my pending application forpa tent Serial No.

211,039, filed May-31, 1938, which has subsequently resulted in U. S.Patent No. 2,166,434,

dated July 18, 1939.

My present invention consists of a new compound or composition ofmatter, consisting of a certain kind of complex amine action between (a)acid esters derived by reobtained from adapted for use as ademulsifier'i n the resolution of crude oil emulsions, either alone, orin admixture with conventional demulsifying agents of a compatible type.It may also have uses inother arts that I have not yet investigated.

In order that the present application may be considered a completedisclosure of my invention,

I deem it advisable to describe the raw materials entering intothemanufacture of my new compound or composition of matter, as well asthe method or procedure employed to produce said compound.

One can obtain or manufacture chemical compounds whose composition isindicated by the following formulas:

oaozm N OIELCnHa R.COO.C2H4

The'compounds above described may besummarized by the following formula:

aooooini)...

in which m represents the number 1 or '2, m

represents the number 1 or 2, sents the number Oorl, with t m--}-m'+m"=3.

and 'm" --repre he proviso that However, the radical Cal-I4, whichappears in the above formula, may represent any similar radical, such asa CSHG radical, CQHB, radical, etc., and therefore, the above formulamay be rewritten:

(onolnmw where n represents -a small .whole number, preferably not over10.

In the above group, T represents a hydrogen atom or a non-hydroxyaliphatic hydrocarbon radical, such as a methyl, ethyl, propyl, amyl, orsimilar radical; or 'I- may represent a non-hydroxy alicyclic radical,such as a cyclohexyl radical, .or a non-hydroxy aralkyl radical, such asa benzyl radical; or the acylated radical'obtained by replacing ahydrogen atom of the hydroxyl group of an alkylol radical by the acylradical of a monobasiccarboxy acid, such as acetic acid, buty-ricaoid,heptoic acid, or the like, allof which are characterized by havingless than -8 carbon atoms. The 'alkylol radical, prior to acylation, maybe a hydroxyjalicyclic or a hydroxy. aralkyl radical, provided thehydroxy radicalis attached to the aliphatic residue of the aralkylradical.

In the above formulaRCOO represents the oxyacyl or acid radical derivedfrom the acid R.COOH. R.COOH represents any monobasic detergentformingcarboxy acid, such as a typical fatty acid or abi'etic acid ornaphthenic acid. Typical fatty acids are'those which occur innaturallyoccurring oils and fats, and generally have eight or morecarbon atoms and not over .32 carbon atoms. Common examples includeoleic acid, stearic acid, linoleic acid, linolenic acid, ricinoleicacid, erucic acid, palmitic acid, myristic acid, etc. These acidscombine with alkali to produce soap or soap-like materials, and arecommonly referred to as being monobasic detergent-forming carboxy acids.Blown oils (oxidized oils) are not included. I

The alkylol radical, previously referred to,.prior to esterification,may be a hydroxy alicyclic or a hydroxy aralkyl radical, provided thehydroxy radical is attached to the aliphatic residue of the aralkylradical.

As to the amines above described, which happen to be tertiary amines, itmay be well to point out that these .may be formed readily by a reactioninvolving an ester of the selected detergent-forming acid, for instance,a fatty acid ester, such as the glyceride, and a corresponding amine.This may be illustrated in the following manner:

Reference is made to co-pending application for patent Serial No.180,993, filed December 21, 1937, by Melvin De Groote, Bernhard Keiser,and Charles M. Blair, J r., which subsequently resulted in U. S. PatentNo. 2,167,349, dated July 25, 1939.

If triethanolamine, as employed in the above formula, is replaced byethyl diethanolamine, then one would obtain one of the remaining typesof tertiary amines illustrated. Reference is made to co-pendingapplication for patent Serial No. 206,904, filed May 9, 1938, by DeGroote, Keiser and Blair.

In the remaining type of material there is an amino hydrogen atompresent. The manufacture of such material may be illustrated by thefollowing reactions:

11.000.C:HAC1+HHNC:H0H-)R.C00.01134 OHCaH:

However, if maximum yields are not necessary, one need not resort toreactions of the kind previously described to produce secondary amines,but one may employ the following type of reaction:

OH.C:H

11.000 011.com

Row-0,111+ NH 11.000 011.com

011.com

3 NH+CaHs(0H)s panolamine,

Suitable primary and secondary amines which may be employed to producematerials of the kind above described include the following,diethanolamine, monoethanolamine, ethyl ethanolamine, methylethanolamine, propanolamine, dipropanolamine, propyl propanolamine, etc.Other examples include cyclohexylolamine, dicyclohexylolamine,cyclohexyl ethanolamine, cyclohexyl propanolamine, benzylethanolamine,benzylpropentanolamine, hexanolamine, octylethanolamine,octadecylethanolamine, cyclo- Y hexanolethanolamine, etc.

Similarly, suitable tertiary amines, which may be employed, include thefollowing: triethanolamine, diethanolalkylamines, such as diethanolethylamine, diethanol propylamine, etc. Other examples include diethanolmethylamine, tripropanolamine, dipropanol methylamine, cyclohexanoldiethanolamine, dicyclohexanol ethanolamine, cyclohexyl diethanolamine,dicyclohexyl ethanolamine, dicyclohexanol ethylamine, benzyldiethanolbenzyl dipropanolamine, tripentanolamine, trihexanolamine,hexyl ethanolamine, octadecyldiethanolamine, polyethanolamine, etc.

It is also known that one may have amines of the type:

CzHrOH Such amines may serve as functional equivalents of the previouslydescribed amines and which are free from an ether linkage.

All of the amines of the kind above described and characterized by theformula:

Boo 0.0m)...

in which m represents the number 1 or 2, m represents the number 1 or 2,and m" represents the number 1, with the proviso that m+m+m"=3; and nrepresents a small whole number, preferably not over 10, have fourcommon characteristics. In the first place, these amines are notquaternary ammonium bases or salts thereof. The expression quaternaryammonium is properly and conventionally applied to compounds in whichall four hydrogen atoms of the ammonium radical NH4 have been replacedby a hydrocarbon radical or oXy-hydrocarbon radical, as, for example, intrimethyl phenyl ammonium hydroxide.

Secondly, an important characteristic which must be recognized is, thatthese amine compounds are not amides. It is to be noted that an amideformation involves a product in which there is a direct linkage betweenthe carboxylic carbon atom and the nitrogen atom in the amine. This isnot the case in the compounds employed as intermediate raw materials forproduction of the compounds used as demulsifying agents in the presentprocess.

In the third place, it must be recognized that these compounds arederived only from basic amines. The word basic is employed to excludeamines having little or no basicity, such as the ordinary aromaticamines, or any amine having at least one aryl radical directly joined tothe with 3 amino nitrogen atom. For this reason, these amine productswhich are herein contemplated as demulsifying agents and which arenecessarily characterized by freedom from any aryl groups, as such,cannot be derived from aryl amines. They are derived solely from alkyl,alicyclic, or aralkyl amines having at least one hydroxyl group present.It is true that in the aralkyl amines there is an aryl group present,but it is not directly attached to the nitrogen atom, as in the case ofaryl amines, but, in fact, represents nothing more or less than asubstituted alkyl-amine. For instance, I consider benzylamine as beingthe primary amine, phenmethyl amine.

Finally, it must be recognized that these materials have not lost anybasicity in the forms of the esterified amine, and that they exhibit allthe properties of a basic amine, that is, they combine with water toform a base, presumably a substituted ammonium compound, but notquaternary ammonium compound insofar that there are always one, two, orthree unsubstituted hydrogen atoms of the ammonium radical present. Theycombine with various acids to form salts. For example, they may becombined with acetic acid, hydrochloric acid, lactic acid, chloraceticacid, nitric acid, butyric acid, phosphoric acid, oxalic acid, or anysuitable organic or inorganic acid, to form salts. It is understood thatthe reference in the specification and appended claims to the aminesincludes the basic form and the acid salts, as well as the aminesthemselves. The new compositions of matter herein described have greatdemulsifying properties which are contributed, in part, by the amine,and it is immaterial whether the amine may be considered as being in anyone of the following forms:

in which T represents the substituents for the amino hydrogen atoms ofthe parent ammonia from which all amines are hypothetically derived, andX simply represents the acid radical of any acid employed.v Thisstatement applies with equal force and effect to the final product, orcomposition of matter, which is also a basic amine of a more complextype.

Reference is again made to the formula which summarizes the variousamines used as intermediate raw materials, viz.:

in which the characteristics have their previous significance.

Attention is directed to the fact that where the substituted alkylradical OH.R.COO.C2H4 appears, a suitable non-aryl radical other than analiphatic residue may serve as the functional equivalent; for instance,an alicyclic radical derived from a cyclohexyl radical, or an aralkylradical derived from a benzyl radical. In other words, in the heretoappended claims reference to the CnHiln radical, as such, or as an alkylradical or residue, is intended in the broad sense to include thealicyclic radicals or residues, or the aralkyl radicals or residueswhich are the equivalent thereof. There is no intention to include anaromatic radical where there is a direct linkage between the aromaticnucleus and the amino hydrogen atom, forthe reason that such productstertiary amine, are not included within the broad class of hy'dro'xytertiary amines, unless there is another hydroxyl radical attached tothe usual alkyl radical. For instance, if ethyl diethanolamine istreated with two moles of lactic acid so as to form the dilactylcompound of the following formula:

g C HaCHC-O-Cgfh on o then it is understood that such materials wouldnot represent a hydroxy tertiary amine within the meaning or scope, asherein employed. If, on the other hand, triethanolamine were treatedwith lactic acid, so as to give monolactyl triethanolamine of thefollowing composition:

then such compound would be included, due to the presence of one or morehydroxyl radicals attached to the alkyl radicals.

Similarly, in indicating the various hydroxylated primary or secondaryamines of the nonaryl type which may be employed to produce the amineherein described, it is desirable to indicate that amines of the typewhere a hydroxy acyl radical replaces a hydrogen atom of the hydroxyradical of a hydroxy primary or secondary amine, are not included withinthe broad class of hydroxy tertiary amines, unless there is anotherhydroxyl radical attached to the usual alkyl radical. For instance, ifethanolamine is treated with lactic acid, so as to form the lactylderivative of the following formula:

then it is understood that such materials would not represent a hydroxyprimary amine within the meaning or scope, as herein employed. The samewould be true if the corresponding product were derived fromdiethanolamine, provided both hydroxy radicals had been esterified withlactic acid. a

The manufacture of compounds from tertiary amines is relatively simple,because no precautions are necessary to prevent amidification. Theselected detergent-forming acid, or ester, as, for example, a fatty oiland the selected hydroxy tertiary amine are mixed in suitableproportions and heated at some point above the boiling point of water,for instance, 110 C., and at a point below the decomposition point ofthe amine or the fatty oil, for instance, 180 C., for a suitable periodof time, such as two to eight hours. Mild agitation is employed. Acatalyst such as sodium oleate, sodium carbonate, caustic soda, etc.,may be present in amounts of about one-half of 1% or less. It is notedthat the fatty acids are employed in this instance in the form of anester, to wit, the glyceride, although, as previously pointed out, otherfunctional equivalents can be readily employed with equal facility. Itis to be noted that the reactions above described do not take place toany appreciable extent if the fatty acid has been converted into thesoap or salt. Such salts are not functional equivalents. As previouslyindicated, an ester of abietic acid might be employed, if desired.

When, however, one is employing a hydroxy secondary amine, precautionsmust be taken, so that one gets a substantial percentage of productsderived by esterification, rather than amidification. Any suitable estermay be employed, but it is often most convenient to employ the glycerideof a fatty acid, for instance, triricinolein.

The selected glyceride and the selected hydroxy secondary amine aremixed in suitable proportions and heated at some point above the boilingpoint of water, for instance, 110 C., and below the decomposition pointof the amine or fatty material, for instance, 180 C., for a suitableperiod of time, such as 4-24 hours. lmld agitation is employed. Acatalyst such as sodium oleate, sodium carbonate, caustic soda, etc.,may be present in amounts of about A.;% or less. It is to be noted thatthe fatty acids are present in ester form and not in the form of thefree acid, and thus there is no tendency to form the salt to any markedextent, and if conducted at the lower range of reaction temperatures,there is a decided tendency to form the esterification products, ratherthan the amidification products.

In order to illustrate suitable examples of the amines which may be usedas intermediate raw materials, the following examples are given:

Intermediate amineEa:ample 1 Castor oil is employed. For sake ofconvenience, its molecular weight is considered as be- Intermediateamine-Example 2 The same procedure is followed as in Intermediate amineExample 1, except that the ratio employed is two moles of the castor oilto three moles of triethanolamine.

Intermediate dmineExample 3 One mole of methyl naphthenate is reacted inthe manner previously described with one mole of triethanolamine.

Intermediate amine-Example 4 Diethanolamine is substituted fortriethanolamine in Example 3.

Intermediate amine-Example 5 Methyl abietate is substituted for methylnaphthenate in Examples 3 and 4 above.

Intermediate amineE:campZe 6 Olive oil is substituted for castor oil inExamples 1 and 2 above.

Intermediate amineE:rample 7 Ethyl diethanolamine is substituted fortriethanolamine in previous examples where triethanolamine has beenemployed, but ratios are changed, if required, so that there is alwaysone non-esterified ethanol radical present.

Intermediate amineE.rampZc 8 Cyclohexyl diethanolamine is substitutedfor triethanolamine in previous examples where triethanolamine has beenemployed, but subject to the same modification as indicated in Example 7immediately preceding.

Intermediate amine-E:Bample 9 Benzyl diethanolamine is substituted fortriethanolamine in previous examples where it has been employed. Seemodification noted in Examples 7 and 8, immediately above.

Intermediate amineE.rampZe 10 Castor oil (triricinolein) is employed.For convenience its molecular weight is considered as being 925.Commercial diethanolamine and castor oil in the proportion of one moleof castor oil to three moles of diethanolamine are heated to atemperature of 120-140" C. for about twelve hours. Mild agitation isemployed. Loss of basicity is an indication of amidification. Time ofesterification may be extended or temperature lowered or raised so as toinsure maximum esterification, and particularly so as to produce aproduct characterized by the presence of one unesterified alkylolradical attached to the amino nitrogen. The reaction product, soproduced, may be used as such, or may be converted into the acetate orother suitable form.

Having prepared the relatively simpler intermediate amines of the kindpreviously described, the second step in the preparation of the newcomposition of matter is to produce acid esters of the kind obtainableby reaction between polybasic carboxy acids or their functionalequivalents, such as the anhydrides and esters of detergent-formingacids or the like. Detergentforming acids are monobasic carboxy acids,such as typical fatty acids, abietic acids, or naphthenic acids. Typicalfatty acids are those which occur in naturally-occurring oils and fatsand generally have 8 or more carbon atoms and not over 32 carbon atoms.Common examples include oleic acid, stearic acid, linoleic acid,linolenic acid, ricinoleic acid, erucic acid, palmitic acid, myristicacid, etc. These various acids combine with alkali to produce soap orsoap-like materials and are commonly referred to as being monobasicdetergent-forming acids. Blown oils (oxidized oils) are not included.

Detergent-forming acids combine with polyhydric alcohols to give esterscharacterized by the p e n o at l as one h d radica attac d to theradical which replaces the carboxylic hydrogen. Polyhydric alcoholsinclude glycerol, ethylene glycol, propylene glycol, and other similarglycols, and also a polyhydroxy ether alcohol type of material such asdiethylene glycol, diglycerol, triglycerol, etc. Such materials, whetherproduced from glycerol or from glycol or from two dissimilar polyhydricalcohols, are characterized by the fact that dehydration produces anoxygen linkage between two organic residues, and thus the material, inaddition to having the properties of a polyhydric alcohol, has to somedegree at least, the properties of an ether.

As to the manufacture of esters from an alcohol, including polyhydricalcohols, and a carboxy acid, the usual procedure is esterification inpresence of dry hydrochloric acid gas. Such method is satisfactory,provided conditions are controlled so that complete esterification doesnot take place, and thus result in a material containing no freehydroxyl in the polyhydric alcohol residue. For example, if diglycerolis esterified with four molecultes of ricinoleic acid, the resultantproduct will not contain a free hydroxy group in the polyglycerolresidue. However, if esterification is continued so that one, two orthree ricinoleic acid residues are introduced, and so that three, two,or one free hydroxyl residues remain in the polyglycerol radical, then asuitable compound is produced. Esterifications to produce the desiredproduct may be conducted in the conventional manner, usually employed insuch reactions.

It is, of course, obvious that esters may be produced as readily fromnaphthenic acid or abietic acid or the like, as from fatty acids. Forsake of brevity, reference will be made particularly to fatty acids. Alarge number of materials derived from fatty acids and characterized bythe presence of a free hydroxyl attached to the hydrocarbon radicalwhich replaces the carboxylic hydrogen, is available in the open marketand sold under the name of superglycerinated fats. Such materials areused as emulsifying agents, both in edible and non-edible products. Theyare derived from a wide variety of acids and a wide variety ofpolyhydric alcohols of both the ether type and the non-ether type.

The following formulas indicate the types derivable fromnon-hydroxylated monobasic carboxy acids:

R.COO.C: 5

If derived from hydroxylated fatty acids, such as hydroxystearic acid,ricinoleic acid, and the like, the above formulas would correspond tothe following:

0H OH.R.C00.Ca s

(OH.R.COO):Ca aOH onncooclmon 05.3.0 0 0.0mm clmon /QH(OH.R.COO)2C|Hn0Ca 5 on OH.R.COO.CaH5 on If such products are reactedwith the polybasic carboxy acid or the anhydride, as, for example,phthalic acid or phthalic anhydride, one can obtain a large number ofesters, which are acidic esters in the sense that there is present afree carboxyl radical. In the following formulas, no attempt is made toshow phthalic anhydride as the usual ortho compound, butit is shown as apara compound, purely for the sake of convenience. The selection ofphthalic acid is purely for purposes of illustration. Any one of anumber of other acids may be employed.

OOC COOH 0oo 3coon R.COO.GaHs

0H ooccoon R.COO.C3H5

oooOcoon /OOCC OOOH R.COO.C3H5

ooo

(R.COO)aCaHuOOC coon noooogmoo 0600011 0 COOH 00C coon C 0 If, however,such materials were derived from hydroxylated fatty acids, withoutinvolving the alcoholiform hydroxyl attached to the fatty acid phthalicanhydride or. its equivalent, so as to proradical, then the aboveformula. would appear as duce reagents indicated by the followingforon.n.coo.c.n..oocooon oocOcoon However, if one considers thereactions in which only the alcoholiform hydroxyl of the fatty acidradical, for example, ricinoleic acid, is involved in formation of thereaction products obtained, then they may be indicated by the followingformulas:

COOH

COOH

R.COO.C;H5

COOH

COOH

R.COO

CaHaOH COOH Similarly, one may have products in which both the alcoholichydroxyl attached to the fatty acid radical and also the hydroxylattached to the glycerol or glycol radical are reacted with mulas:

coon

on R.0OO.CH

' oocOcoon coon ooc coon R.coo.c3H5

ooc coon coon cznl.ooc coon R.COO

coon

coon accommoocOcoon In the examples shown above, where the ester ispolybasic, one might remove the acidity of one of the carboxylichydrogen atoms, or two of the carboxylic hydrogen atoms in any feasiblemanner, that is, by neutralization with an alkali or by conversion intoan ester involving a reaction with any suitable alcohol, i. e., amonohydric, trihydric, etc. In any event, however, the material derivedby reaction between a polybasic acid or its functional equivalent andthe hydroxylated ester type of fatty material of the kind described, isalways characterized by the presence of at least one free carboxylradical.

Where reference is made to ricinoleic acid, hydroxy-stearic acid,abietic acid, and the like, it is evident that certain simplederivatives, such as the halogenated compounds, are the obviousfunctional equivalents; for instance, chlorinated ricinoleic acid, maybe employed instead of ricinoleic acid; brominated oleic acid might beemployed instead of oleic acid; hydrogenated abietic acid might beemployed instead of abietic acid. In these instances, the monobasicdetergentforming carboxy material, notwithstanding modifications of thekind indicated, still has the same functional properties as theunmodified material; and thus acts in the same manner, as far aschemical reactions noted are concerned, and also as far as producing aneffective demulsifying agent is concerned.

In the hereto appended claims, reference to monobasic detergent-formingcarboxy acids includes such obvious functional equivalents.

As to the manufacture of reagents from polybasic carboxy acids andsuperglycerinated fats or the like, it need simply be stated that thesereagents have been produced and used in the arts as plasticizers,demulsifying agents, etc.; and that the method of producing the same iswell known. Briefly stated, esterification takes place readily on theapplication of heat, and the reaction may be hastened by employing ahigher temperature, provided the decomposition does not take place; orthe reaction may be conducted in presence of an inert solvent, such asxylene, which may be removed after completion of reaction.

The reaction can be hastened also by passing, through the mixture adried inert gas; or the reaction may be conducted under a refluxcondenser using material such as xylene and a water trap, so as toremove water as quickly as formed. Generally speaking, however, thereactions take place rapidly, quickly, and completely by simply heatingthe products together in stoichiometric proportions at a temperaturesomewhere above the boiling point of water, and particularly at atemperature of about -1GO 0., provided there is no decomposition.Phthalic acid is particular" ly suitable, because it does not decomposereadily, whereas, some other acid, such as oxalic acid, may be readilydesirable, but the temperature of esterification must be lower, ofcourse, to prevent decomposition.

The polybasic acids which may be employed, including some having atleast threecarboxyl radicals, are phthalic, succinic, malic, fumaric,

citric, maleic, adipic, tartaric, glutaric, diphenic,

naphthalic, oxalic, etc.

It is to be noted that the manufacture of the composition of matter inreality involves three dififerent esterification reactions. For example,a fatty acid may be reacted with a tertiary hydroxyamine to giveproducts of the kind indicated. Naturally, if the tertiary amine, suchas triethan- Ola-mine, is reacted with a glyceride, the reaction may, inessence, be a rearrangement reaction, rather than an esterificationreaction, although for purposes of classification, it may be consideredas an esterification reaction. The second estcrification reactioninvolved is the one between the hydroxy fatty body of the kinddescribed, such as super-glycerinated fats and phthalic anhydride, orthe like. Monoabietin or mononaphthenin, of course, may be consideredbroadly as a superglycerinated fat.

The third esterification reaction is between the two types of materialsabove described, the simpler amine always being characterized by thepresence of an alcoholic hydroxyl radical, and the ester beingcharacterized by the presence of the carboxyl group. The last mentionedesterification reaction goes readily and is nothing more or less than aconventional esterification reaction and requires no furtherelaboration.

Composition of mutton-Example 1 One employs an intermediate amine of thekind described under Intermediate amine Example 1 above. Commercialdiricinolein is treated with two moles of phthalic anhydride, so as toyield an ester having two free carboxyl radicals. One molecular weightof this acidic ester is reacted with one mole of material exemplified byIntermediate amine Example l, so as to yield a product characterized bythe presence of both free carboxyl radicals and free alcoholic hydroxylradicals. This is a conventional esterification reaction, and thematerials are intermittently mixed and heated at approximately mil- C.,with constant agitation. until samples taken from the batch and analyzedshow substantially complete reaction. A suitable solvent may be present,and water formed may be distilled off continuously during theesterification process. The solvent may remain behind in the finalproduct or be removed, if desired.

' Composition of matter-Example 2 Diphthalated mono-olein is substitutedfor diphthalated diricinolein in Composition of matter Example 1,immediately above.

Composition of mattcrEmample 3 Dimaleated monostearin is substituted fordiphthalated diricinolein in Composition of matter Example 1 above.

Composition of matier-Erample 4 Dioxalated mono-abietin is substitutedfor diphthalated diricinolein in Composition of matter Example 1 above.

Composition of matter-Example 5 Dicitrated mononaphthenin is substitutedfor diphthalated diricinolein in Composition of matter Example 1 above.

Composition of matter-Example 6 An amine of the kind characterized bythe product described under Intermediate amine Example l0is substitutedin the above Composition of matter Examples 1-5 for the intermediateamine therein employed.

It should be noted, however, that this particular product contains onlytwo hydroxyl radicals available for esterification per atom of nitrogen.Insofar that some amidification may take place in following thedirections in preparing the amine from diethanolamine in Intermediateamine Example 10 above, it is probably the safest procedure to determinethe acetyl or hydroxyl value before reacting in molecular proportions.

Attention is directed to the fact that the alkylolamines are obtained insuch a manner that they maybe looked upon as being derivatives ofdihydric alcohols, for instance, the chlorhydrin of the dihydricalcohol, as indicated in the following manner:

mammjilj-Eriirrm As previously stated, the C2H4 radical may be any oneof a number of hydrocarbon radicals which are aliphatic, alicyclic, oraralkyl in nature.

It is at once manifest that similar derivatives are available fromglycerols, polyglycerols, and the like, as indicated by the followingreaction:

(omzoansip'jffjimm It is not necessary to point out that the same typesof reactions Will produce secondary or tertiary amines and that thereaction is not limited to a combination with ammonia, but may takeplace with a combination of otherprimary or secondary amines, such asamylamine, diamyl amine, cyclohexylamine, dicyclohexylamine,benzylamine, dibenzylamine, amylcyclohexylamine, etc.

This means that in the type of material previously described, there is awide variety of material, such as monoglycerylamine, diglycerylamine,monoglyceryl diethanolamine, monoglyceryl dipropylamine, diglycerylpropylamine, triglycerylaminc, etc, which are functional equivalents ofthe various amines previously described for reaction with triricinoleinand the like.

When such amines are employed, instead of the radical -CnH2nappearing ina compound, one would have in place thereof the radical OEC3H5; or, incase the hydroxyl radical of these -OH.C3H5 radical had been removed byesterification with any available carboxyl, then the substituent whichreplaces the CnH2nradical might be indicated by the formula D.C3H5. Allthat has been said here in regard to functional equivalents willbeperfectly 0bvious without further explanation to those skilled in theart. See U. S. Patent No. 2,091,704, dated August; 31, 1937, to Duncanand McAllister, and also U. S. Patent No. 2,042,621, dated June 2, 1936,to Olin.

Similarly, it is evident that where reference is made to phthalic acid,some simple derivative, such as chlorinated phthalic acid, brominatedphthalic acid, methylated phthalic acid, or the like, would simply actas a functional equivalent. This applies not only to phthalic acid, butall the dibasic acids enumerated.

Similarly, it is evident that there is no intention to differentiatebetwen isomeric forms. One isomeric form may serve as well as another.Attention is particularly called to the last two examples above, whichare characterized especially by the presence of a free carboxyl radicalother than the carboxyl radical derived from dibasic acid. Needless tostate, in the reaction between the ester derived by reaction between apolybasic carboxy acid material and a selected fatty material of thekind described, if there be a carboxyl radical attached to a fatty chainavailable for esterification, as well as a carboxyl attached to thedibasic acid, then in such event, if there is sufficlent availablehydroxyl radicals attached to the amine of the kind previouslydescribed, both types of carboxyl radicals, i. e., (a) a carboxylradical attached to a polybasic carboxy acid residue; and (b) a carboxylradical attached to a fatty acid residue may enter into the reaction.However, my experience is that the carboxy] radical attached to thepolybasic carboxyl acid residue is generally more reactive and entersinto reaction in preference to the other type of carboxyl radical,although both reactions may take place simultaneously to at least alimited degree.

I desire to emphasize that any of the products obtained in the aboveexamples, when employed as a demulsifier in the resolution of crude oilemulsions, may be used in the form of the amine by direct contact withan emulsion, without contact with water. It may be contacted with water,i. e., in the form of a solution, so as to produce in a greater orlesser degree the amine base. Furthermore, any of the products abovedescribed may be combined with a suitable acid. Acetic acid may beemployed. Hydrochloric acid is particularly desirable. In some instancesacids, such as oleic acid or naphthenic acid, may be employed to give asuitable salt. As previously pointed out, any carboxylic hydrogen atommay be replaced by a suitable metallic atom, or an organic radicalderived from an alcohol or from an amine. All such ionizable hydrogenatom equivalents are considered as the functional equivalent of theionizable hydrogen atoms themselves, and such neutralized forms areincluded in the scope of the appended claims as the equivalents of theacidic form. The expression fatty acid compound is employed to includethe acid itself, as well as salts and esters thereof. It is realizedthat where a free carboxyl and a basic amine residue exists in the samemolecule, there may be a tendency towards the formation of inner saltscomparable to sulfanilic acid; but due to the size of the moleculeinvolved, and perhaps for reasons of steric hindrance, I am not awarethat such inner salts are formed.

Briefly, then, the preparation of the composition of matter hereincontemplated depends on a reaction involving a polybasic carboxy acidbody, or its functional equivalent, as described, and the complex amineof the kind described, in

such a manner as to involve reactions other than salt formation. Inother words, the complex amines are basic in nature, and therefore,could react with a polybasic acid to form a salt in a manner which, forsake of convenience, will be indicated by a somewhat simpler reaction,thus:

COOH (R)xN+T COOH Such reactions are purely salt formation. Thematerials of the kind herein contemplated, regardless of their nature,are of the kind obtained by reactions other than salt formation, andalso other than amidification.

I desire to emphasize that the expression polybasic carboxy acid, as itappears in the claims, refers not only to the acid itself, but to anyfunctional equivalent, such as the anhydride, the acyl chloride, 2. saltform having at least two free carboxyls, such as mono-sodium citrate,etc. It is also understood that in the hereto appended claims the natureof the final product is not limited to the form having a free carboxylichydrogen, but that such free carboxylic hydrogen may actually bereplaced by any functional equivalent of the kind previously described,for instance, a metallic atom, an ammonium radical, an amine radical,such as an amylamine radical, benzylamine radical, ethanolamine radical,diethanolamine radical, triethanolamine radical, a hydrocarbon radical,such as an ethyl, methyl, propyl, or amyl radical, a radical derivedfrom ethylene glycol, glycerol, or the like; a cyclohexyl radical,benzyl radical, etc. All such forms in which such ionizable hydrogenatom equivalent replaces an ionizable hydrogen atom, are obviousfunctional equivalents.

Attention is directed to the fact that the word amidification has beenapplied to the reaction involving the replacement of an amino hydrogenatom by an acyl radical, without conventional limitation to a reactioninvolving ammonia. The replacement of the amino hydrogen atom of aprimary amine, or a secondary amine by an acyl radical has beenconsidered as being amidification, rather than the formation of asubstituted amide, or the formation of an irnide or substituted imide.Such obvious departure from conventional nomenclature has been forpurposes of simplicity and to show the similarity between certainreactions.

It is desirable to emphasize again that in the hereto appended claimsreference to a polybasic carboxy acid includes not only the acid itself,but also various salts and esters thereof, and also other functionalequivalents, such as the anhydrides, acyl chlorides, etc. Furthermore,in the hereto appended claims, reference to the product derived byreaction between an acid ester of the kind previously described and anamine of the kind previously described, is meant to refer to suchproducts in all its various modifications previously referred to, towit, such instances where carboxylic hydrogen atoms appear as such, orhave been replaced by metallic atoms, organic radicals derived fromvarious alcohols, amine radicals, or residues, etc.; and as to thepresence of any basic amine nitrogen atom, it may be in the amine form,or in a salt form, or in a base form, as, for example, obtainable bycontact with water. The functional equivalents of all these variationshave been pointed out previously and were readily comprehended; and thescope of .the claims, in the light of such obvious equivalents, requiresno further discussion.

As to blown oils, blown fatty acids, polymerized oils, polymerized fattyacids, and other similar materials obtained by oxidation, it is notintended that they should be reacted with amines to produce theintermediate amine, which, in turn, is reacted with the acidic esterderived, in part, from a polybasic carboxy acid.

In considering the compositions of matter herein disclosed, at least tothe extent that they are derived from basic diols, it is necessary toappreciate that such substances are not resins in the sense that suchterm is used to indicate materials which are obtained from the same rawmaterials combined in different proportionsand under differentconditions of reaction. The simplest resin formation may be, exemplifiedby the reaction between ethylene glycol and phthalic acid. The productof such reaction may be indicated by the following formula:

In such resins 11. represents a fairly large whole number. It is obviousthat if one hydroxyl of triethanolamine has been esterified with amonobasic carboxy acid, that the resultant product indicated, aspreviously stated, by the following formula may conveniently beconsidered as a diol.

oHonnNonEnoH Similarly, such a product can form a resin comparable toone obtained from the commonest diol, to wit: ethylene glycol and wouldbe indicated thus:

OH[C2H4NC2H4O COO o o] n 0211,0003 If a monoglyceride. be denoted,thus:

, on R.COO.Ca s

and a diglyceride be denoted in the following it becomes obvious thatphthalated derivatives thereof may be indicated thus:

, oocooon R.COO.CaH

on oooooon R.COO.Ca 5

oooOooon (R.COO)5O:H50OCC COOH ethanolamine with a mole of a fatty acidthe product reacts readily with phthalio anhydride under properconditions-to produce a resinous material, as previously indicated. Suchresinous material may be modified by introduction of a fatty acid, so asto stop further growth by reacting with the available hydroxyl. Such material as a resin would be comparable to a modificd special alkyd resin.

If however, phthalic anhydride, as such, is not used in the free state,but instead, is used in. a state where one carboxyl has been united witha hydroxylated fatty body, such asa monoglyceride,

or a diglyceride, or the like, as previously described, then suchmaterials are apt to be monobasic, and hence, not resin-forming.However, even where they are dibasic, they do'not react to produceresins, and do not build up molecules of a resinous nature inconjunction with basic diols, for various reasons, some of which areapparent and-some of which are not. place, steric hindrances possiblyprevent random contact. In the second place, the basicity of thenitrogen atom tends to form inner salts. space distances betweencarboxyl radicals becomes large in terms of the intervening atoms orradicals. The alcoholic hydroxyls of the partially esterified glycerylradical, or similar radicals,

The

In the first is characterized by the fact that there is also attachedthereto another long chain monobasic carboxy' acid radical which mayhave an interfering effect to a marked degree. molecular reactionsreally involve three-dimension components, and the final product is ofthree dimensions. Chemical formulae, as above employed, are at bestlimited to two dimensions. It is difilcultto contemplate such complexreaction of actual three-dimensional combinations based on structuralformulae of two dimensions only. However, enough has been said in thisdiscussion to enable one to realize that the compounds hereincontemplated, particularly when derived from basic diols, should not beconfused with resinous materials.

For convenience, in the present instance the expression diol has beenused in referenceto the material derived by an esterification of onehydroxyl triethanolamine, or the like. Similarly, the expressiontrihydrlc will be conveniently used to indicate combinations that haveat least three alcoholic hydroxyl radicals, and thus would includematerials which actually have more than three; for instance, materialswhich have four or more hydroxyl radicals obtained, for instance, byderivatives of dihydroxy stearic' acid, or from glycerylaniines, orboth. Obviously, a polybasic Finally, the V carboxy acid having morethan two carboxylradicals still acts as if it only had two carboxyradicals in such instances where one of such radicals has been renderedinactive byesterification or salt formation, as in the instance ofmonosodium salt of citric acid, to which previous reference has beenmade.

The method of using the herein described compound or composition ofmatter to resolve a petroleum emulsion of the water-imoil type isclearly disclosed in my parent application Serial No. 211,039, filed May31, 1938, which has subsequently resulted in U. S. Patent No. 2,166,434,dated July 18, 1939, of which the present application is a continuationin part.

Having thus described my invention, what I claim as new and desire tosecure by Letters Patent is: v

1. The product resulting from an esterifioation reaction between (A) anamine of the formula type:

acoopnnh)...

(OH.OnH2n) in which R.COO represents the oxy-acyl radical derived from amonobasic detergent-forming carboxy acid; T represents a member of theclass consisting of hydrogen atoms, hydrocarbon radicals and non-hydroxyacylated radicals obtained by replacing a hydrogen atom of the hydroxylgroup of an alkylol radical by the acyl radical of a monobasic cal-boxyacid having less than 8 carbon atoms; n represents a small whole numberwhich is less than 10; m represents the numeral 1 or 2; m" representsthe numeral 1 or 2, and m" represents the numeral or 1; with the provisothat m+m+m"=3; and (B) an acidic ester derived by reaction between apolybasic carboxy acid and a hydroxylated ester of a monobasicdetergent-forming carboxy acid; said hydroxylated ester containing atleast one hydroxyl radical attached to the alcohol residue; and saidacidic ester being characterized by the presence of at least onecarboxyl radical.

2. The product resulting from an esterification reaction between (A) anamine of the formula type:

in which R.COO represents the oxy-acyl radical derived from a monobasicdetergent-forming carboxy acid; T represents a member of the classconsisting of hydrogen atoms, hydrocarbon radicals and non-hydroxyacylated radicals obtained by replacing a hydrogen atom of the hydroxylgroup of an alkylol radical by the acyl radical of a monobasic carboxyacid having less than 8 carbon atoms; n represents a small whole numberwhich is less than m represents the numeral 1 or 2; m represents thenumeral 1 or 2; and m" represents the number 0 or 1; with the provisothat m+m+m"=3.; and (B) an acidic ester derived by reaction between adibasic carboxy acidKand a hydroxylated ester of a monobasicdetergent-forming carboxy acid; said hydroxylated ester containing atleast one hydroxyl radical attached to the alcohol residue; and saidacidic ester being characterized by the presence of at least onecarboXyl radical.

3. The product resulting from an esterification reaction between (A) anamine of the formula type:

in which H.000 represents the oXy-acyl radical derived from a monobasicdetergent-forming carboxy acid; T represents a member of the classconsisting of hydrogen atoms, hydrocarbon radicals and non-hydroxyacylated radicals obtained by replacing a hydrogen atom of the hydroxylgroup of an alkylol radical by the acyl radical of a monobasic carboxyacid having less than 8 carbon atoms; CnHZn is an aliphatic radical; nrepresents a small whole number which is less than 10; m represents thenumeral 1 or 2; m represents the numeral 1 or 2, and m represents thenumeral 0 or 1; with the proviso that m+m'+m"=3; and (B) an acidic esterderived by reaction between a dibasic carboxy acid and a hydroxylatedester of a monobasic detergent-forming carboxy acid; said hydroxylatedester containing at least one hydroxyl radical attached to the alcoholresidue; and said acidic ester being characterized by the presence of atleast one carboxyl radical.

4. The product resulting from an esterification reaction between (A) anamine of the formula type:

in which R.COO represents the oXy-acyl radical derived from a fattyacid; T represents a member of the class consisting of hydrogen atoms,hydrocarbon radicals and non-hydroxy acylated radicals obtained byreplacing a hydrogen atom of the hydroxyl group of an alkylol radical bythe acyl radical of a monobasic carboxy acid having less than 8 carbonatoms; CnHZn is an aliphatic radical; n represents a small whole numberwhich is less than 10; m represents the numeral 1 or 2; m represents thenumeral 1 or 2, and m" represents the numeral 0 or 1; with the provisothat m+m+m=3; and (B) an acidic ester derived by reaction between adibasic carboxy acid and a hydroxylated ester of a monobasicdetergent-forming carboxy acid; said hydroxylated ester containing atleast one hydroxyl radical attached to the alcohol residue; and saidacidic ester being characterized by the presence of at least onecarboxyl radical.

5. The product resulting from an esterification reaction between (A) anamine of the formula type:

in which RCOO represents the oXy-acyl radical derived from ahydroxylated fatty acid; T represents a member of the class consistingof hydrogen atoms, hydrocarbon radicals and non-hydroxy acylatedradicals obtained by replacing a hydrogen atom of the hydroxyl group ofan alkylol radical by the acyl radical of a monobasic carboxy acidhaving less than 8 carbon atoms; C1LH21L is an aliphatic radical; nrepresents a small whole number which is less than 10; m represents thenumeral 1 or 2, m represents the numeral 1 or 2; and m" represents thenumeral 0 or 1; with the proviso that m+m'+m"=3; and (B) an acidic esterderived by reaction between a dibasic carboxy acid and a hydroxylatedester of a monobasic detergent-forming carboxy acid; said hydroxylatedester containing at least one hydroxyl radical attached to the alcoholresidue; and said acidic ester being characterized by the presence of atleast one carboxyl radical.

6. The product resulting from an esterification reaction between (A) anamine of the formula type:

in which OHRCOO represents the oxy-acyl radical derived from ahydroxylated fatty acid; m represents the numeral 1 or 2; m representsthe nmneral 1 or 2; with the proviso that m+m'=3; and (B) an acidicester derived by reaction between a dibasic carboxy acid and ahydroxylated ester of a monobasic detergent-forming carboxy acid; saidhydroxylated ester containing at least one hydroxyl radical attached tothe alcohol residue; and said acidic ester being characterized by thepresence of at least one carboxyl radical.

7. The product resulting from an esterification reaction between (A) anamine of the formula type:

in which OHRCOO represents the oxy-acyl radical derived from ricinoleicacid; m represents the numeral 1 or 2; m represents the numeral 1 or 2;with the proviso that m+m' =3; and (B) an acidic ester derived byreaction between a dibasic carboxy acid and a hydroxylated ester of amonobasic detergent-forming carboxy acid; said hydroxylated estercontaining at least one hydroxyl radical attached to the alcoholresidue; and said acidic ester being characterized by the presence of atleast one carboxyl radical.

8. The product resulting from an esterification reaction between (A) anamine of the formula type:

in which OH.RCOO represents the oxy-acyl radical derived from ricinoleicacid; m represents the numeral 1 or 2; m represents the numeral 1 or 2;with the proviso that m+m'=3; and (B) an acidic ester derived byreaction between phthalic anhydride and a hydroxylated ester of amonobasic detergent-forming carboxy acid; said hydroxylated estercontaining at least one hydroxyl radical attached to the alcoholresidue; said acidic ester being characterized by the presence of atleast one carboxyl radical.

MELVIN DE GROO'IE.

. CERTIFICATE OF CORRECTION. Patent No. 2,19ll,6ll6. March 26, l9L O.

MELVIN DE GROOTE'.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows: Page 2,first column, lines 29 and 50, strike out the comma and words whichsubsequently resulted in U. 3. Patent No. 2,167,5L 9, dated July 25,1959" and insert the same after "Blair" and before the period in line57; lines 61 to 61;,

in the formula, for

"OI-LC H OH.C H

2 LR read 2 OH.C H OH.C H

page 5, first column, line 21;, for "molecultes" read --molecules-; andthat the said Letters Patent should be read with this correction thereinthat the same may conform to the record of the case in the PatentOffice.

Signed and sealed this 50th day of July, A, D. 1911.0.

Henry Van Arsdale,

(Seal) Acting Commissioner of Patents.

